Metal salts of succinamic acids in distillate fuel oil



United States Patent 3,264,075 METAL SALTS 0F SUCCINAMIC ACIDS INDISTILLATE FUEL OIL Paul Y. C. Gee, Woodbury, and Harry J. Andress, Jr.,Pitman, N..l., assignors to Mobil Oil Corporation, a corporation of NewYork No Drawing. Filed July 6, 1962, Ser. No. 208,127 The portion of theterm of the patent subsequent to Apr. 24, 1979, has been disclaimed 4Claims. (Cl. 44-68) This invention relates to the improvement ofnonlubricating fractions. It is more particularly concerned withdistillate fuel oils containing additives adapted to inhibit theappearance of sediment during prolonged storage periods, to preventscreen-clogging, prevent rusting of ferrous metal surfaces, and toinhibit the fuel oils against emulsification.

It is well known that fuel oils are prone to form sludge or sedimentduring periods of prolonged storage. This sediment, of course, has anadverse effect on burner operation, because it has a tendency to clogscreens and nozzles. In addition to sediment formed during storage, mostfuel oils contain other impurities, such as rust, dirt, and entrainedwater. The sediment and impurities tend to settle out on equipmentparts, such as nozzles, screens, filters, etc., thereby clogging themand causing the equipment to fail.

A further factor, incident to the storage and handling of fuel oils, isthe breathing of storage vessels. This results in the accumulation ofconsiderable amounts of water in the tanks, which presents a problem ofrusting in the tanks. Then, when the oil is removed for transportation,sufficient water may be carried along to cause rusting of ferrous metalsurfaces in pipelines, tankers, and the like.

Generally, it has been the practice to overcome the aforedescribeddifiiculties with a separate additive for each purpose, i.e., with asediment inhibitor, an antiscreen clogging agent, and an antirust agent.The use of several additives, however, gives rise to problems ofadditive compatibility, thus restricting the choice of additivecombinations. In addition, of course, the use of a plurality ofadditives unduly increases the cost of the fuel.

It has now been found that all three problems, i.e., sedimentation,screen clogging, and rusting, can be solved by the use of a single fueloil addition agent. It has been discovered that a distillate fuel oilcontaining minor amounts of certain metal salts of certain amic acidsare effectively inhibited, simultaneously, against all threeaforementioned difliculties and, of considerable importance, withoutinducing objectionable emulsification characteristics to the distillatefuel oils.

Accordingly, it is a broad object of this invention to provide a fueloil having properties improved with a minimum number of addition agents.Another object is to provide a fuel oil having a single additive adaptedto inhibit sedimentation, to prevent screen clogging, and to preventrusting of ferrous metal surfaces with which it comes in contact. Aspecific object is to provide a fuel oil containing certain metal saltsof amic acids that achieves these results. Other objects and advantagesof this invention will become apparent to those skilled in the art fromthe following detailed description.

The present invention provides a distillate fuel oil containing a minoramount, sufficient to inhibit sedimentation and screen clogging, .and toprevent rusting of ferrous metal surfaces in contact therewith withoutinducing objectionable emulsification characteristics to said fuel oil,of a compound selected from the group consisting of (l) a metal salt ofa succinamic acid having the formula: (I) CHr-CHz M RHN o :1 wherein Ris a monovalent aliphatic hydrocarbon radical having between about 4 andabout 30 carbon atoms and a tertiary carbon atom linked to the nitrogenatom; M is a metal selected from the group consisting of divalentcopper, and metals from Groups HA, 1113, IIIA, IVA, and VIII of thePeriodic Chart of the Elements, and n is a small Whole number equal tothe valence of M; (2) an alkoxy metal salt of succinamic acid having theformula:

wherein R, R and M have the aforesaid significance, and n is an integerof l to 5, or more, such as 1 to 10, and preferably 1 to 6.

The addition agents utilizable in the fuel oil compositions of thisinvention are metal salts of amic acids that have the formula:

CHz-CHz l 0 COOH wherein R is an aliphatic hydrocarbon radical of analiphatic, primary tertiary alkyl amine containing between about 4 andabout 30 carbon atoms and a tertiary carbon atom attached to thenitrogen atom. The amic acids contemplated herein can be made by anymethod for preparing such compounds that is known to the art. They areproduced, preferably, by warming succinic acid anhydride with a primarytertiary-alkyl amine having between about 4 and about 30 carbon atomsper molecule to form the monoamide of the acid. This can be done readilyby heating the mixture of anhydride and amine at a temperature of 65-al50 C. for a period of time varying between one and 3 hours. Theaddition occurs readily without the formation of water. Less desirably,the amic acids can be prepared by the controlled reaction betweensuccinic acid and the amine, with the elimination of one mole of waterper mole of amic acid produced. Care must be exercised to avoid theelimination of two moles of water to form the cyclic imide.

The amines that can be utilized to form the amie acids are the tertiaryalkyl, primary, monoamines in which a primary amino(-NH group isattached to a tertiary a carbon atom; and mixtures thereof. These aminesall contain the terminal group,

Non-limiting examples of the amine reactants are t-butyl primary amine,t-hexyl primary amine, t-octyl primary amine, t-decyl primary amine,t-dodecyl primary amine, t-tetradecyl primary amine, t-octadecyl primaryamine, t-eicosyl primary amine, t-tetracosyl primary amine, andt-triacontyl primary amine. The amine reactants can be prepared inseveral ways well known to those skilled in the art. Specific methods ofpreparing the t-alkyl primary amines are disclosed in the Journal ofOrganic Chemistry, vol. 20, page 295 et seq. (1955). Mixtures of suchamines can be made from a polyolefin fraction (e.g., polypropylene andpolybutylene cuts) by first hydrating with sulfuric acid and water tothe corresponding alcohol, converting the alcohol to alkyl chloride withammonia, under pressure, to produce the t-alkyl primary amine mixture.

The salts of the succinamic acids contemplated herein are metal saltswherein the salt-forming vmetal is an appropriate metal from Groups IB,IIA, IIB, IIIA, IVA and VIII of the Periodic Chart of the Elements, asset forth in Introductory College Chemistry by H. G. Deming (John Wileyand Sons). Preferred salt-forming metals are cupric Cu, Ba, Ca, Sr, Mg,Zn, Cd, Al, Pb and Fe. The method of forming the metal salts of thisinvention is not a critical factor herein. Thus, any of the usualmethods known to those skilled in the art can be utilized. Typicalmethods for forming the normal salt (Formula I) include forming analkali-metal salt (e.g., by neutralizing with caustic), and then using adouble decomposition reaction with a salt of the desired metal (e.g.,CuSO neutralizing the acid with a metal alcoholate (e.g., bariummethylate); and heating with an oxide of the metal (e.g., magnesiumoxide). Suitably, the non-polar solvents can be used in thesalft-forming operation. In many cases, the metal salts of thisinvention can be used in solution in the solvent, for greater ease ofhandling. Thus, concentrates of the salts of this invention in amountsvarying between 10% and about 90%, by weight, in a solvent arecontemplated. Such concentrates are then added to the fuel oil to givethe desired final concentration in the fuel. Suitable solvents arebenzene, toluene, xylene, light lubricating oil, Sovasol #5 andkerosene. The alkoxy metal salts (For mula II) can be prepared byheating one mole of the succinamic acid with one mole of an appropriateM(O- alkyl) compound (e.g., magnesium methylate); and the complex alkoxymetal salts (Formula III) can be prepared by heating the succinamic acidwith two or more moles of the stated M(O-alkyl) compound.

The fuel oils that are improved in accordance with this invention arehydrocarbon fractions having an initial boiling point of at least about100 F. and an end boiling point no higher than about 750 F., and boilingsubstantially continuously throughout their distillation range. Suchfuel oils are generally known as distillate fuel oils. It is to beunderstood, however, that this term is not restricted to straight-rundistillate fractions. The distillate fuel oils can be straight-rundistillate fuel oils, catalytically or thermally cracked (includinghydrocracked) distillate fuel oils, or mixtures of straight-rundistillate fuel oils, naphthas and the like with cracked distillatestocks. Moreover, such fuel oils can be treated in accordance with wellknown commercial methods, such as, acid or caustic treatment,hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively lowviscosities, pour points, and the like. The principal property whichcharacterizes the contemplated hydrocarbons, however, is thedistillation range. As

mentioned hereinbefore, this range will lie between about 100 F. andabout 750 F. Obviously, the distillation range of each individual fueloil will cover a narrower boiling range falling, nevertheless, withinthe above-specified limits. Likewise, each fuel oil will boilsubstantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2, and 3 fueloils used as heating and diesel fuel oils, and jet combustion fuels. Thedomestic fuel oils generally conform to the specifications set forth inASTM Specifications D396-48T. Specifications for diesel fuels aredefined in ASTM Specifications D975-48T. Typical jet fuels are definedin Military Specification MIL-F- 5624B.

The amount of the metal salt of succinamic acid that is added to thedistillate fuel oil in accordance with this invention will depend uponthe intended purpose and the particular amic acid salt selected, as theyare not all equivalent in their activities. Some may have to be used ingreater concentrations than others to be effective. In most cases, inwhich it is desired to obtain all three beneficial results, namely, toinhibit sedimentation, to reduce screen clogging, and to prevent rustingof ferrous metal surfaces, additive concentrations varying between 10pounds per thousand barrels of oil and about 200 pounds per thousandbarrels of oil will be employed. It may not always be desired, however,to accomplish all three aforementioned results. In such cases, where itis desired to effect only one or two results, lower concentrations canbe used. Thus, if it is desired only to prevent rust under dynamicconditions, as in a pipeline, it has been found that concentrations aslow as about 5 ppm, i.e., about one pound of additive per thousandbarrels of oil, are effective. In general, therefore, the amount ofmetal salt of amic acid that can be added to the distillate fuel oil, inorder to achieve a beneficial result, will vary generally between aboutone pound per thousand barrels of oil and about 200 pounds per thousandbarrels of oil. Preferably, it will vary between about 10 and about 200pounds per thousand barrels of oil.

If it is desired, the fuel oil compositions can contain other additivesfor the purpose of achieving other results. Thus, for example, there canbe present foam inhibitors and ignition and burning quality improvers.Examples of such additives are silicones, dinitropropane, amyl nitrate,metal sulfonates, and the like.

The following specific examples are for the purpose of illustrating thefuel oil compositions of this invention, and of exemplifying thespecific nature thereof. It is to be strictly understood, however, thatthis invention is not to be limited by the particular additives and fueloils, or to the operations and manipulations described therein. Otheramic acid salts and fuel oils, as discussed hereinbefore, can be used,as those skilled in the art will readily appreciate.

The amine reactants used in the specific working examples are mixturesof pure amines. Amine A is a mixture of primary amines having a carbonatom of a tertiary butyl group attached to the amino (NH group andcontaining 12 to 15 carbon atoms per amine molecule and averaging 12carbon atoms per molecule. This mixture contains, by weight, aboutpercent tertiary-dodecyl primary amine, about 10 percenttertiarypentadecyl primary amine, and relatively small amounts, i.e.,less than about 5 percent of amines having less than 12 or more than 15carbon atoms. Amine B is a mixture of tertiary-alkyl primary aminescontaining 18 to 24 carbon atoms per molecule and averaging about 20carbon atoms per molecule. It has a tertiary carbon atom attached to theNH group and contains, by weight, about 40 percent tertiary-octadecylprimary amine, about 30 percent tertiaryeicosyl primary amine, about 15percent tertiary-docosyl primary amine, about 10 percenttertiary-tetracosyl primary amine, and a small amount, less than 5percent, other amines as high as tertiary-triacontyl primary amine.

C. to form the Ca salt.

Saybolt at 100 F., and a viscosity index of 105.

EXAMPLE 1 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 300 gms. of Sovasol #5 as a diluent wasstirred at 85-100 C. for approximately 2 hours to form the Amine Asuccinamic acid. To the above Amine A succinamic acid was added at roomtemperature with stirring 69 gms. (0.25 mole 6 gms. excess) of CuSO -5HO previously dissolved in 100 cc. of water and then 21 gms. (0.5 mole 1gm. excess) of NaOH previously dissolved in 100 cc. of water. Themixture was stirred at 100 C. for 6 hours. The reaction product wasseparated from the water layer and filtered by gravity. The finalproduct, the copper salt of the Amine A succinamic acid, which contained66%% Sovasol #5 was fluid at room temperature.

Analysis.-Percent Cu, 1.72; percent N, 1.32.

EXAMPLE 2 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 100cc. of benzene as a diluent wasstirred at 85 C. for 2 hours to form the Amine A succinamic acid. TheAmine A succinamic acid was then added at room temperature with stirringto 6 gms. (0.25 mole) of Mg in the form of a Mg methylate solution. Themixture was gradually heated to 150 C. to distill out the methanol. Thereaction product, the Mg salt of Amine A succinamic acid, being viscous,was diluted with 312 gms. of xylene and filtered through filteringclays. The final product which contained 66 /a% xylene was clear andfluid at room temperature.

Analysis.-Estimated: Percent Mg, 1.28; percent N, 1.50. Found: PercentMg, 1.28; percent N, 1.59.

EXAMPLE 3 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene as a diluent wasstirred at 95 C. for 2 hours to form the Amine A succinamic acid. To theabove Amine A succinamic acid was added at room temperature withstirring 286 gms. of 12% Ba methylate solution (equivalent to 0.25 moleof Ba). The mixture was gradually heated to 175 C. to distill out thesolvent. The reaction product, the Ba salt of Amine A succinamic acid,being viscous, was diluted with 736 gms. of xylene and filtered throughfiltering clay. The final product which contained approximately 80%xylene was clear and fluid at room temperature.

Analysis-Estimated: Percent Ba 3.2; percent N 0.7. Found: Percent Ba,2.98; percent N, 0.72.

EXAMPLE 4 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 200 cc. of toluene was stirred at 85 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 20 gms. (0.5mole) of NaOH dissolved in 200 cc. of methanol. The mixture wasgradually heated to 175 C. to form the sodium salt of Amine A succinamicacid. To the sodium salt of Amine A succinamic acid was then added atroom temperature 33 gms. (0.25 mole 5 gms. excess) of CaCl previouslydissolved in 200 cc. of methanol. The mixture was gradually heated to175 The reaction product being viscous, was diluted with 200 cc. ofbenzene, filtered through filtering clay and topped to 175 C. underhouse vacuum. The final product, the Ca salt of Amine A succinamic acid,weighed 150 gms. and was diluted with 150 gms. of xylene.

Analysis.-Estimated: Percent Ca, 3.15; percent N, 2.2. Found: PercentCa, 3.23; percent N, 2.28.

EXAMPLE 5 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene was stirred at C. for 2hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 20 gms. (0.5mole) of NaOH dissolved in 200 cc. of methanol. The mixture wasgradually heated to 175 C. to form a sodium salt of the Amine Asuccinamic acid. To the sodium salt of Amine A succinamic acid was thenadded at room temperature: 44 gms. (0.25 mole 10 gms. excess) of ZnCldissolved in 200 cc. of methanol. The mixture was gradually heated to175 C. to form a Zn salt of the Amine A succinamic acid. The reactionproduct was diluted with 500 cc. of benzene, filtered through filteringclay and topped to C. under house vacuum to remove the benzene. Thefinal product, the Zn salt of the Amine A succinamic acid, which weighed156 gms. was viscous and diluted with 156 gms. of xylene.

Analysis.Estimated: Percent Zn, 5.02;- percent N, 2.10. Found: PercentZi, 5.05; percent N, 1.90.

EXAMPLE 6 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 100 cc. of toluene Was stirred at 95 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 11.5 gms.0.5 mole) of sodium in the form of a sodium methylate solution. Themixture was gradually heated to 150 C. and was held at 150 C. for 2hours to insure the complete formation of the sodium salt of the Amine Asuccinamic acid. To the sodium salt of the Amine A succinamic acid wasthen added at rom temperature with stirring 30 gms. (Ma mole+3 gms.excess) of ferric chloride dissolved in 200 cc. of methanol. The mixturewas gradually heated to 150 C. and was held at 150 C. for 3 hours.Thereaction product was diluted with 200 cc. of benzene, filteredthrough filtering clay and topped to 60 C. under a pressure of 3' mm. ofmercury. The final product, the iron salt of Amine A succinamic acid,which weighed 147 gms. was viscous at room temperature and diluted with147 gms. of Xylene.

An alysis.-Estim atedz percent Fe, 2.9; percent N, 2.2. Found: percentFe, 3.42; percent N, 2.25.

EXAMPLE 7 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 4.5 gms.mole) of aluminum in the form of an aluminum butylate solution. Themixture was gradually heated to 175 C. to form the aluminum salt of theAmine A succinamic acid. The reaction product was diluted with 500 cc.of benzene, filtered through filtering clay and topped -to 150 C. underthe house vacuum. The final product which weighed gms. was viscous anddiluted with 130 gms. of xylene.

Analysis.Estimated: percent A1, 1.4; percent N, 2.3. Found: percent Al,1.25; percent N, 2.37.

EXAMPLE 8 A mixture of 50 gms. (0.5 mole) of succinic anhydride, gms.(0.5 mole) of Amine B and 150* cc. of xylene was stirred at 95 C. for 4hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at room'temperature with stirring 6 gms. (0.25mole) of Mg in the form of a Mg methylate solution. The mixture wasgradually heated to 175 C. to form the Mg salt of Amine B succinamicacid. The reaction product being viscous, was diluted with 206 gms. oflight lubricating oil and filtered through filtering clay.

Analysis-Estimated: percent Mg, 1.34; percent N, 1.7. Found: percent Mg,1.49; percent N, 1.87.

EXAMPLE 9 A mixture of 50 gms. (0.5 mole) of succinic anhydride, .150gms. (0.5 mole) of Amine B and 150 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at room temperature with stirring 20' gms.(0.5 mole) NaOH previously dissolved in 200 cc. of methanol. The mixturewas gradually heated to 175 C. to form the sodium salt of the Amine Bsuccinamic acid. To the Na salt of the Amine B succinamic acid was thenadded 420 gms. of light lubricating oil and 33 gms. (0.25 mole+ gms.excess) of CaCl previously dissolved in 200 cc. of methanol. The mixturewas gradually heated to 175 C. and was held there for 3 hours to insurethe complete formation of the Ca salt. The reaction product was filteredthrough filtering clay. The final product, the calcium salt of the AmineB succinamic acid, which contains 66%% light lubricating oil was fluidat room. temperature.

Analysis.Estimated: percent Ca, 1.85; percent N, 1.32. Found: percentCa, 1.57; percent N, 1.12.

EXAMPLE 10 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 150 cc. of toluene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at 50 C. with stirring 286 gms. of 12% Bamethylate solution (0.25 mole of Ba). The mixture was gradually heatedto 175 The reaction product being viscous, was diluted with 468 gms. oflight lubricating .oil and filtered through filtering clay. The finalproduct,

EXAMPLE 11 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 150 cc. of xylene was stirred at 95 C.for 2. hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid Was added at room temperature with stirring gms. (0.5mole) of NaOH previously dissolved in 250 cc. of methanol. The mixturewas gradually heated to .175" C. to form the Na salt of the Amine Bsuccinamic acid. To the Na salt of the Amine B succinamic acid was thenadded at room temperature with stirring 432 gms. of light lubricatingoil and 44 gms. (0.25 mole+10 gms. excess) of ZnOl previously dissolvedin 250 cc. of methanol. The mixture was gradually heated to 175 C. andwas held at 175 C. for 3 hours to insure the complete formation of theZn salt of the Amine B succinamic acid. The product was filtered throughfiltering clay. The final product which contained 66%% light lubricatingoil was fluid at room temperature.

Analysis.-Estimated: percent Zn, 2.5; percent N, 1.08.

Found: percent Zn, 2.91; percent N, 1.08.

EXAMPLE 12 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B, 206 gms. of light lubricating oil and 100cc. of benzene was stirred at 95-l00 C. for 2 hours to form the Amine Bsuccinamic acid. To the above Amine B succinamic acid was added at roomtemperature with stirring 10.08 gms. (0.25 mole) of MgO previously mixedwith 20 cc. of water to form a paste. The mixture was gradually heatedto 175 C. and was held at 175 C. for 2 hours. The reaction product wasthen filtered through filtering clay. The final product, the Mg salt ofthe Amine B succinamic acid, which contained 50% light lubricating oilwas fluid at room. temperature.

Analysis.Estimated: percent Mg, 1.4; percent N, 1.7. Found: percent Mg,1.24; percent N, 1.58.

EXAMPLE 13 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B, 206 gms. of light lubricating oil and 100cc. of benzene was stirred at 100 C. for 2 hours to form the Amine Bsuccinamic acid. To the above Amine B succinamic acid was added at roomtemperature with stirring 14.6 gms. (0.25 mole) of Mg(OH) The mixturewas gradually heated to 175 C. and was held at 175 C. for 30 minutes.The product was then filtered through filtering clay. The final product,the Mg salt of Amine B succinamic acid, which contained 50% lightlubricating oil was fluid at room temperature.

Analysis.Estimated: Percent Mg, 1.4; percent N, 1.7. Found: Percent Mg,1.28; percent N, 1.52.

EXAMPLE 14 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 250 cc. of xylene was stirred at C. for 2hours to form the Amine B succinamic acid. The Amine B succinamic acidwas then added at room temperature with stirring to 11.5 gms. (0.5 mole)of Na in the form of a Na methylate solution. The mixture was graduallyheated to 150 C. and was held at 150 C. for 2 hours to insure thecomplete formation of the Na salt of Amine B succinamic acid. The Nasalt, diluted with 750 cc. of benzene, was then added at roomtemperature with stirring to 76.5 gms. (0.25 mole 7 gms. excess) of PbCldissolved in 2500 cc. of distilled water. The mixture was stirred at C.for 8 hours to insure the complete formation of the lead salt. The leadsalt was separated from the water layer, filtered through Hyflo clay andtopped to C. under house vacuum. The final product, the lead salt ofAmine B succinamic acid, which weighed 228 gms., theory 252 gms. wasviscous at room temperature and diluted with 228 gms. of xylene.

Analysis.Estimated: Percent Pb, 10.0; percent N, 1.3. Found: Percent Pb,9.7; percent N, 1.53.

EXAMPLE 15 A mixture of 150 gms. (0.5 mole) of Amine A succinamic acid,diluted with 150 gms. of Solvesso #150, and 12 gms. (0.5 mole) of Mg inthe form of a Mg methylate solution was gradually heated to 150 C. toremove the methanol. The reaction product, being viscous, was dilutedwith 150 gms. of toluene and filtered through Hyflo clay. The finalproduct, the methoxy Mg salt of Amine A succinamic acid, which contained66%% solvent was clear and fluid at room temperature.

Analysis.Estimated: Percent Mg, 2.6. Found: Percent Mg, 2.8.

EXAMPLE 16 A mixture of 50 gms. (0.5 mole) of succinic anhydride and 150gms. (0.5 mole) of Amine B was heated with stirring at 100105 C. for 1%hours to form the Amine B succinamic acid. The Amine B succinamic acid,diluted with 600 gms. of Solvesso #150, was added at room temperaturewith stirring to 24.32 gms. (1 mole) of Mg in the form of a Mg methylatesolution. The mixture was gradually heated with stirring. At 82 C. thereaction mixture started to thicken but became fluid after a quantity of15 cc. of water was added. The reaction mixture to remove the methanol.

was then heated to 130 C. to remove the methanol. The final product, thecomplex methoxy Mg salt of Amine B succinarnic acid, which contained 4equivalents of Mg and 73% Solvesso #150 was clear and fluid at roomtemperature.

Analysis.-Estimated: Percent Mg, 2.9. Found: Percent Mg, 2.81.

EXAMPLE 17 A mixture of 150 gms. (0.5 mole) of Amine A succinamic acid,diluted with 450 gms. of Solvesso #150, and 24.32 gms. (1 mole) of Mg inthe form of a Mg methylate solution was gradually heated to 120 C. toremove the methanol. The final product, the complex methoxy Mg salt ofAmine A succinamic acid, which contained 4 Mg equivalents and 72%Solvesso #150 was clear and fluid at room temperature.

Analysis-Estimated: Percent Mg, 3.8. Found: Percent Mg, 3.38.

EXAMPLE 18 A mixture of 50 gms. 0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 600 gms. of S01- vesso #150 as a diluentwas heated with stirring at 95- 105 C. for 2 hours to form the Amine Bsuccinamic acid. The Amine B succinamic acid was then added at roomtemperature with stirring to 36.5 gms. (1.5 mole) of Mg in the form of aMg methylate solution. The mixture was gradually heated with stirring.At 80 C. the mixture started to thicken but became fluid after aquantity of cc. of water had been added. The reaction mixture was thengradually heated to 130 C. to remove the methanol. The final product,the complex methoxy Mg salt of Amine B succinamic acid which contained 6Mg equivalents and 72% Solvesso #150 was clear and fluid at roomtemperature.

Analysis.-Estimated: Percent Mg, 4.3. cent Mg, 4.02.

Found: Per

EXAMPLE 19 A mixture of 150 gms. (0.5 mole) of Amine A succinamic acid,diluted with 450 gms. of Solvesso #150, and 36.48 gms. (1.5 moles) ofmagnesium in the form of a Mg rnethylate solution was gradually heatedwith stirring. At 82 C. before thickening occurred, a quantity of cc. ofwater was added dropwise to the mixture. The mixture was then graduallyheated to 125 C. The final product, the complex methoxy Mg salt of AmineA succinamic acid, which contained six Mg equivalents and 72% Solvesso#150 was clear and fluid at room temperature.

Analysis-Estimated: Percent Mg, 5.7. Found: Percent Mg, 5.42.

Sedimentatio n.The test used to determine the sedimentationcharacteristics of the fuel oils is the 100 F. Storage Test. In thistest, a SOO-milliliter sample of the fuel oil under test is placed in aconvected oven maintained at 110 F. for a period of 12 weeks. Then, thesample is removed from the oven and cooled. The cooled sample isfiltered through a tared asbestos filter (Gooch crucible) to removeinsoluble matter. The weight of such matter in milligrams is reported asthe amount of sediment. A sample of the blank, uninhibited oil is runalong with a fuel oil blend under test. The effectiveness of a fuel oilcontaining an inhibitor is determined by comparing the weight ofsediment formed in the inhibited oil with that formed in the uninhibitedoil.

EXAMPLE 20 i the blended fuels and uninhibited fuels are set forth inTable I. The test fuel oil is a blend of 60 percent distillate stockobtained from continuous catalytic cracking and 40 percent straight-rundistillate stock. It has a boill0 ing range of between about 320 F. andabout 640 F. and is a typical No. 2 fuel oil.

Table l FUEL OIL STORAGE TEST-1;3\ I 1%VE WEEKS STORAGE AT InhibitorConcn. lb./ Sediment,

1,000 bbls. rug/liter Uninhibited fuel blend 0 104 Uniuhibited fuelblend plus Ex. 2.-.. 50 26 Uninhibited fuel blend 0 Uninhibited fuelblend plus Ex. 3 50 18 Uninhibited fuel blend 0 104 Uninhibited fuelblend plus Ex 8 50 24 Uninhlbited fuel blend- 0 100 Uninhibited fuelblend plus E 50 94 Uninhibited fuel blend 0 100 Uninhibited fuel blendplus Ex. 10 50 41 Uninhibited fuel blend 0 25 Uninhibited fuel blendplus Ex. 11 10 18 Uninhiblted fuel blend 0 79 Uninhibited fuel blendplus Ex 12 50 24 Uniuhibited fuel blend 0 79 Uninhibited fuel blend 5035 Uninhibited fuel blend 0 10 Uninhibited fuel blend plus Ex. 1 25 5Uninhibited fuel blend 0 79 Uninhibited fuel blend plus Ex. 15. 50 2Uninhibited fuel blend 0 46 Uninhibited fuel blend plus Ex 18 10 9Uninhibited fuel blend O 46 Uninhibited fuel blend plus Ex. 25 6 Screenclogging-The anti-screen clogging characteristics of a fuel oil weredetermined as follows: The test is conducted using a Sundstrand V3 or S1home fuel oil burner pump with a self-contained 100-mesh Monel metalscreen. About 0.05 percent, by Weight, of naturallyformed fuel oilsediment, composed of fuel oil, Water, dirt, rust, and organic sludge ismixed with 10 liters of the fuel oil. This mixture is circulated by thepump through the screen for 6 hours. Then, the sludge deposit on thescreen is washed off with normal pentane and filtered through a taredGooch crucible. After drying, the material in Gooch crucible is washedwith a 50-50 (volume) acetone-methanol mixture. The total organicsediment is obtained by evaporating the pentane and the acetone-methanolfiltrates. Drying and weighing the Gooch crucible yields the amount ofinorganic sediment. The sum of the organic and inorganic deposits on thescreen can be reported in milligrams recovered or converted into percentscreen clogging.

EXAMPLE 21 Using the test fuel oil described in Example 20, blends ofadditives from the foregoing examples in this fuel were prepared. Eachblend was subjected to the Screen Clogging Test, as aforedescribed. Testresults are set forth in Table II.

Table II SCREEN OLOGGING TESTS Inhibitor Conen. lb./ Screen 1,000 bbls.Clogging,

Percent .Uninhibited fuel blend 0 100 Uninhibited fuel blend plus Ex. 259 Uniuhibited fuel blend plus Ex. 25 27 Uninhibited fuel blend plus Ex.50 7 Uninhibited fuel blend plus Ex. 10 10 Uninhibited fuel blend plusEx 50 21 Unmhlbited fuel blend plus Ex 50 47 Unmhlbited fuel blend plusEx 25 30 Uninhlbited fuel blend plus Ex. 25 27 Uninhibited fuel blendplus Ex. 50 23 Uninhibited fuel blend plus Ex. 10 9 Uninhibited fuelblend plus Ex. 25 24 Uninhibited fuel blend plus Ex. 25 2 Uninhlbitedfuel blend plus Ex. 3 25 3 Uniuhibited fuel blend plus Ex. 50 9Uninhibited fuel blend plus Ex. 50 2 Uninhibited fuel blend plus Ex. 102 Uninhibited fuel blend plus Ex. 10 5 Rusting.The method used fortesting anti-rust properties of the fuel oils was ASTM Rust Test D-665operated 1 1 for 48 hours at 80 F. using distilled water. This is adynamic test that indicates the ability to prevent rusting of ferrousmetal surfaces in pipelines, tubes, etc.

EXAMPLE 22 Blends of additives described in Examples 1 through 15 in thefuel oil of Example 20 were subjected to the ASTM Rust Test D-665.Pertinent data are set forth in Table III.

Table III A-STM RUST TEST D-665 Inhibitor Conen, Rust Test p.p.m. ResultBlank fuel blend Fail.

Blank fuel blend plus Ex 10 Pass.

Blank fuel blend plus Ex. 10 Do. Blank fuel blend plus Ex. 10 Do. Blankfuel blend plus Ex. 5 Do. Blank fuel blend plus Ex. 5 Do. Blank fuelblend plus Ex. 10 D0. Blank fuel blend plus Ex. 10 D0. Blank fuel blendplus Ex. 10 Do. Blank fuel blend plus Ex. 25 D0. Blank fuel blend plusEx. 25 Do. Blank fuel blend plus Ex. 25 Do. Blank fuel blend plus Ex. 10Do. Blank fuel blend plus Ex. 10 Do. Blank fuel blend plus Ex. 25 Do.Blank fuel blend plus Ex. 5 Do.

It will be apparent, from the data set forth in Tables I through III,that the metal salts of the succinamic acids of this invention arehighly effective to reduce sedimentation and screen clogging and toinhibit rusting of ferrous metal surfaces under static or dynamicconditions. As is to be expected, results will vary among specificmaterials used. In order to accomplish any given improvement, many ofthe additives can be used in relatively small amounts, as for dynamicrust prevention. If, on the other hand, it is desired to accomplish allthe aforementioned :beneficial results, this can be accomplished by useof relatively larger concentrations of the additive.

Over and above the aforesaid improvements imparted to distillate fueloil compositions by the addition agents embodied herein, such additionagents also function as inhibitors against objectionableemulsifications. In that "respect, the presence of the tertiary carbonatom linked to the nitrogen atom in the amide grouping of the metalsalts embodied herein is important as, for corresponding metal salts butin which the nitrogen atom is linked to a normal aliphatic group, suchsalts induce severe emulsification with water. In example, reference ismade to Example 23 showing preparation of a magnesium salt of asuccinamic acid derived from a normal amine (Armeen 12D) which is amixture of primary amines containing 2% decylamine, 95% dodecyla-mineand 3% tetradecyl amine. To illustrate the importance of a tertiarycarbon atom linked to the nitrogen atom in the additives embodied hereinfor inhibiting emulsification, fuel oil compositions were prepared byaddition of the metal salt (Mg) of Example 2, the metal salt (Ba) ofExample 3, and the metal salt (Mg) of Example 23 in concentration of 50lbs./ thousand barrels of the fuel oil and the resulting compositionswere subjected to the emulsion test described hereinafter.

Example 23 A mixture of 33 /3 gms. /3 mole) of succinic anhydride, 65gms (Va mole) of Armeen 12D and 205 gms. of xylene as diluent was heatedat 95 C. for 2 hours with stirring to form the Armeen 12D succinamicacid. The

-Armeen 12D succinamic acid was then gradually added Armeen 12Dsuccinamic acid, which contained 75% solvent (50% xylene+25%isopropanol), was clear and fluid at room temperature.

Anaylsz's.-Estimated: percent Mg, 0.97; percent N, 1.15. Found: percentMg, 1.2; percent N, 1.29.

Emulsion test.The procedure for the fuel oil emulsion test is asfollows: a 200 milliliter portion of the fuel to be tested and 20milliliters of distilled water are placed in a clear glass pint bottle.The bottle is tightly capped and set in an Everbach mechanical shaker ina horizontal. position such that the maximum degree of agitation isafforded. The shaker is run at its maximum setting for 5 minutes. Thebottle is then removed and allowed to stand in an upright position inthe dark for 24 hours. At the end of the 24 hour settling period, theappearance of the water layer is noted. The fuel layer is siphoned off,care being taken not to disturb the oil-water interface, and isdiscarded. A fresh portion of the fuel oil being tested is then added.The described sequence of steps is repeated. If no emulsion appears inthe water layer after this sequence has been performed ten times, theoil is considered to have passed the test. On the other hand, if, afterany 24 hour settling period in the procedure, there is any degree ofemulsification in the water layer, the fuel is considered to have failedthe test. This test procedure has been found to provide emulsions ininhibited oils similar to emulsions which occur in these same oils onlyafter prolonged periods of normal handling and storage in the field on acommercial basis.

RATING SCALE FOR REPORTING EMULSION TEST RESULTS Description of EmulsionClean break on the interface of oil and water. No dirt,

skin, or bubbles present.

Very slight skin at the oil-water interface that usually does not breakon tilting the bottle.

Skin at oil-water interface, heavier than #1 and usually accompaniedwith dirt and bubbles on the skin. No evidence of any white emulsion.

First sign of white emulsion. Usually forms at the bottom and in thecenter of the bottle. It is circular in shape and approximately M to 1inch in diameter.

Approximately the same amount of emulsion on the bottom of the bottle as#3. However, emulsion is also beginning to form at oil-water interfaceand extends lz to Ms downward into the water layer. Roughly 15% of waterlayer occupied by emulsion.

Circular emulsion at bottom of bottle extends outward and upwardresembling spokes. Emulsion at the interface a little thicker than #4.

More emulsion than #5. Thin film of emulsion forming on sides of bottlesurrounding the water layer. Water is still visible looking through thesides and looking up from the bottom of the bottle.

Emulsion on bottom of water layer is almost solid. Emul sion on sides ofbottle is broken in a few spots enabling the operator to see the Waterlayer.

Semi-solid emulsion with perforations or bubbles similar to a honeycomb.No water visible except that seen in the bubbles.

Same emulsion as #8 but with less bubbles. 75-90% emulsion is solid.

Almost completely solid emulsion with only a few air bubbles visible.

Completely solid emulsion (Mayonnaise type).

The results obtained from the foregoing emulsion test were as follows:

Base Fuel Additive Rating Base FueL. Ex. 2 2 Base FueL. Ex. 3 2

Base FueL. Ex. 23 9 out departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchvariations and modifications are considered to be Within the purview andscope of the appended claims.

What is claimed is:

1. A petroleum distillate fuel oil containing a small amount, sutficientto inhibit said oil against sedirnentation, screen clogging,emulsification and rusting of ferrous metal surfaces in contacttherewith, of a compound from the group consisting of (1) a metal saltwherein R is a monovalent aliphatic hydrocarbon group having between 4-and 30 carbon atoms and a tertiary carbon atom linked to the nitrogenatom; M is a metal from the group consisting of divalent copper andmetals from Groups HA, IIB, IIIA, IVA and VIII, and n is a whole numberequal to the valence of M; (2) an allcoxy metal salt of the formula:

ll CHz-O-NHR canoe, and (3) a complex alkoxy metal salt of the followingformula:

wherein R, R and M have the aforesaid significance, and n is an integerof 1 to 10 2. A fuel oil as defined in claim 1, containing said compoundin an amount of from about one to about 200 pounds per thousand barrelsof oil.

3. A fuel oil, as defined in claim 1, wherein R contains from 1 to 18carbon atoms.

4. A fuel oil, as defined in claim 1, wherein n is an integer of 1 to 5and R is methyl.

References (Cited by the Examiner 5 DANIEL E. WYMAN, Primary Examiner.

wherein R is a saturated aliphatic hydrocarbon group, M is a divalentmetal and R has the aforesaid signifi- JULIUS GREENWALD, Examiner.

W. E. SCHULZ, I. E. DEMPSEY, Assistant Examiners.

Disclaimer 3,264,075.Paul Y. 0. Gm. Voodbur and Harry J. Andress. J in,Pit'man,

N .J. METAL SALTS OF UCCINAMIC ACIDS IN DISTIL- LATE FUEL OIL. Patentdated Aug. 2, 1906. Disclaimer filed Nov. 20, 1968, by the assignee,Mobil Oil Corporation. Hereby disclaims the terminal portion of the termof the patent subsequent to Apr. 24, 1979.

[Ofiicz'al Gazette April 1, 1.969.]

1. A PETROLEUM DISTILLATE FUEL OIL CONTAINING A SMALL 3TATION, SCREENCLOGGING, EMULSIFICATION AND RUSTING OF AMOUNT, SUFFICIENT TO INHIBITSAID OIL AGAINST SEDIMENFERROUS METAL SURFACES IN CONTACT THEREWITH, OFA COMPOUND FROM THE GROUP CONSISTING OF (1) A METAL SALT OF THE FORMULA: